Nitrogen-containing cyclic silanes, their preparation and hydrolysis



United States Patent 3,146,250 NITROGEN-CGNTAINENG CYCLIC SILANES, TIEIR PREPARATIQN AND ROLYSIS John L. Speier, Midland, Mich, assignor toDow Corning Corporation, Midland, Mich, a corporation of Michigan NoDrawing. Filed Oct. 11, 1961, Ser. No. 144,297

. 19 Claims. (Cl. 260-4482) This invention relates to new and usefulnitrogen-containing cylic silanes, methods for their preparation andmethods for making nitrogen-containing siloxanes from these compounds.

It is an object of the present invention to prepare novelnitrogen-containing cyclic silanes. Another object is to preparesiloxanes from these silanes. It is a further object to use these cyclicsilanes to endblock diorganosiloxanes.

The novel nitrogen-containing cyclic silanes of this invention have thegeneral formula (RNR(SiRz wherein R is selected from the groupconsisting of hydrogen atoms, monovalent hydrocarbon, monovalenthydrocarbon radicals containing oxygen in the form of imil linkages,aminoalkyl, aminophenyl, halogenophenyl and organosilyl radicals of thegeneral formula (XR-) Y Si wherein Y is a monovalent hydrocarbon radicaland X is selected from the group consisting of halogen atoms having anatomic weight of at least 35 and hydrogen atoms, R is a divalentsaturated aliphatic hydrocarbon radical wherein the silicon atom isattached to a carbon atom which is at least the third and not more thanthe sixth carbon atom away from the other substituent attached to R andR" is selected from the group consisting of monovalent hydrocarbon,monovalent hydrocarbon radicals containing oxygen in the form oflinkages, alkoxy, alkoxy radicals containing oxygen in the form of a? Olinkages and phenoxy radicals.

R in the above formula can be a hydrogen atom. R can also be amonovalent hydrocarbon radical. Specific examples of such radicals arealkyl radicals, such as methyl, ethyl, t-butyl and octadecyl; alkenylradicals, such as vinyl, allyl and butadienyl; cycloalkyl radicals, suchas cyclobutyl, cyclopentyl, cyclohexyl; cycloalkenyl radicals, such ascyclopentenyl and cyclohexenyl; aryl radicals, such as phenyl and xenyl;aralkyl radicals, such as benzyl and xylyl and alkaryl radicals, such astolyl. R can be a monovalent hydrocarbon radical containing oxygen inthe form of l linkages. Specific examples of such radicals are CH CH OCHCH CH OCH CH and CH OC H R can be an aminoalkyl radical such asaminomethyl, aminoethyl, aminohexyl and aminooctyl. R can also be anaminophenyl radical. R can be a halo genophenyl, such as p-ClC I-I andm-BrC H R can also be an organosilyl radical of the formula radical,such as ClCH CH(CH )CI-l wherein Y is a monovalent hydrocarbon radical(suitable examples have been set forth previously) and X is a hydrogenor a halogen atom having an atomic weight of at least 35 (i.e. chlorine,bromine and iodine). R in the XR' group is a divalent saturatedaliphatic hydrocarbon radical wherein the silicon atom is attached to acarbon atom which is at least the third and not more than the sixthcarbon atom away from the X group attached to R. Thus, the XR- group canbe an alkyl radical such as CH CH CH CH (CH CH CH (CH CH and CH (CH CH abranched alkyl radical such as CH CH(CH )CH halogenoalkyl radicals, suchas ClCH CH CH BrCH CH CH ICH CH CH CICH (CH CH ClCH (CH CH and ClCH (CHCH or a branched halogenoalkyl As indicated above, there must be in theR group at least 3 and not more than 6 carbon atoms between the siliconatom and X.

R in the is a divalent saturated aliphatic hydrocarbon radical whereinthe nitrogen atom is attached to a carbon atom which is at least thethird and not more than the sixth carbon atom away from the siliconatom. Suitable examples of R are CH CH CH --CH (CH CH and CH2(CH2)4CH2.The R group can also be a branched alkylene group as long as there areat least 3 and not more than 6 carbon atoms between the silicon atomandthe nitrogen atom. Suitable examples of such branched alkylene groupsare and CH CH[(CH )CH ]CH CH CH R can be a monovalent hydrocarbon(suitable examples are set forth above); monovalent hydrocarbon radicalscontaining oxygen in the form of l l linkages (suitable examples are setforth above); alkoxy radical, such as methoxy, ethoxy and butoxy; alkoxyradicals containing oxygen in the form of linkages, such as --OCH CH OCH-OCH CH CH OCH CH and -OCH OCH CH or a phenoxy radical.

There are several methods for preparing the above cyclic silanes. Thosecyclic silanes which contain no (XR)Y Siradicals can be prepared byelfecting a reaction between (1) a halogenoalkylhalogenosilane of theformula R2 (XR) SiX and (2) an amino compound of the formula RNH R is adivalent saturated aliphatic hydrocarbon radical wherein the siliconatom is attached to a carbon atom which is at least the third and notmore than the sixth carbon atom away from the other substituent attachedto R. R is a monovalent hydrocarbon, monovalent hydrocarbon radicalcontaining oxygen in the form of 450th l l linkages, aminoalkyl,aminophenyl or halogenophenyl radical. Suitable examples of theseradicals are set forth above. R is as defined above. X can be achlorine, bromine or iodine atom.

After the reaction has been concluded, the hydrogen halide produced isremoved and the resultant product is separated by distillation or othersuitable means. The amount of amino compound employed for this reactionshould be suflicient to react with all the halogen atoms in thehalogenoalkylhalogenosilane (1). It is usually desirable that thereaction be conducted using an excess of the amino compound since thispermits easier separation of the pure product, because the aminocompound acts as a hydrogen halide acceptor. If desired, inert hydrogenhalide acceptors such as tributylamine, pyridine and quinoline can besubstituted in place of some of the excess amino compound intended as ahydrogen halide acceptor. It is preferable to use between 7 and 10 molsof ithe amino compound (2) 'per mol of (1 The cyclic silanes of thisinvention which contain no (XR'-)Y Si-- groups can be prepared byheating a silane of the general formula (RNHR')Si(R) (OZ) R can be ahydrogen atom, monovalent hydrocarbon, monovalent hydrocarbon radicalcontaining oxygen in the form of -oo( I I linkages, aminoalkyl,aminophenyl or halogenophenyl radical. R is as defined above. R" is amonovalent hydrocarbonradical or a monovalent hydrocarbon radicalcontaining oxygen in the form of an I I linkages. Z is a phenyl, alkylor an alkyl radical containing oxygen in the form of linkages. Thesubscript a has a value of from to 2 inclusive. One of the OZ groups iseliminated as an alcohol of the formula HOZ during the course of thisreaction resulting in a product of the general formula It is necessarythat a temperature in excess of 100 C. be employed in this reaction.Generally, temperatures near the boiling point of the alkoxysilane arepreferred. If desired, the alcohol produced during the reaction can beremoved as the reaction proceeds. It was most unexpected that one OZgroup would be cleaved and a cyclic formed upon heating (RNHR'.)Si(R")(OZ) A method for making the cyclic silanes of this invention whichcontain a (XR')Y Sigroup is to react a disilazane of the formulaHN[Si(R") (RX)] with ammonia. R is a monovalent hydrocarbon radical. Xis a chlorine, bromine or iodine atom. R is a divalent saturatedaliphatic hydrocarbon radical attached to a carbon atom which is atleast the third and not more than the sixth carbon atom away from thehalogen atom attached to R. Suitable examples of such XR'- groups areClCH CH(CH )CH BrCH CH(CH )CH and ICH CH(CH )CH This reaction producestwo products. One product has the general formula (HNR')Si(R)z The otherproduct has the formula This reaction can be carried out at varioustemperatures. Generally, temperatures between 100 C. and 200 C. arepreferred. The reaction can be conducted within a wide range ofatmospheric and superatmospheric pressures. Superatmospheric pressuresare preferred for faster and more complete reaction. The ammonium halideproduced during this reaction is best separated by filtration.

4 The compound HN[Si(R") (--RX)] is produced by effecting a reactionbetween ammonia and no alkoxy or phenoxy radicals can be hydrolyzed andcondensed to produce disiloxanes. The cyclic compounds which containeither alkoxy or phenoxy radicals can be hydrolyzed and condensed toproduce either linear or crosslinked siloxanes depending upon the numberof alkoxy and/or phenoxy groups attached to each silicon atom. Thesiloxanes produced from the cyclic silanes of this invention have theunit formula RI! (RNHn')si0 These siloxanes are made by hydrolyzing andcondensing a compound of the general formula (RNR)Si(R)a(OZ)2-n whereinR is selected from the group consisting of hydrogen atoms, monovalenthydrocarbon, monovalent hydrocarbon radicals containing oxygen in theform of I I COC- I I linkages, aminoalkyl, aminophenyl, halogenophenyland organosilyl radicals of the formula (XR')Y Si Wherein Y is amonovalent hydrocarbon radical and X is selected from the groupconsisting of halogen atoms having an atomic weight of at least 35 andhydrogen atoms, R' is a divalent saturated aliphatic hydrocarbon radicalwherein the silicon atom is attached to a carbon atom which is at leastthe third and not more than the sixth carbon atom away from thesubstituent attached to R, R" is selected from the group consisting ofmonovalent hydrocarbon and monovalent hydrocarbon radicals containingoxygen in the form of linkages, Z is selected from the group consistingof alkyl and phenyl radicals and alkyl radicals containing oxygen in theform of linkages and a has a value of from 0 to 2 inclusive.

These organosilicon polymers can be employed as a basis for rubbers,resins and oils. These nitrogen-containing siloxanes are useful ascorrosion inhibitors in corrosive solutions that are in contact withsteel. These nitrogen-containing siloxanes are useful as curing agentsin polyurethane resins.

The cyclic silanes of this invention can be reacted with hydroxyendblocked diorganosiloxanes to produce a siloxane which is endblockedwith units containing nitrogen attached to silicon through a divalentsaturated aliphatic hydrocarbon radical. These endblocked diorganosiloxanes are produced by effecting a reaction between and A product ofthe formula RI! R!!! l (R NHR) S1 510 I ll! kill a Ball stirred afterthe addition.

6 EXAMPLE 2 Quantitative yields of the following siloxanes were obtainedby adding to the following diorganosilicon compounds at a ratio of 2mols of the cyclic compound per one mol of the diorgansilicon compound.In each case the mixture was In each case approximate values for thedegree of polymerization of the diorganosilicon compound and thesiloxane product are given.

Table I Diorganosilieon SilOxane product compound 6 5) H? 1.... HOSiOHCHaNHCHzCH(OH OH S iO Si(O H )g ($0115) 1:53.... 2

CH CH CH3 "CH 2.--- HO(S iO )H CHaNHCH2CH(CHs)CHgS iO EiiOSiCH2CH(CHa)CHzNHC1-I H3 3 5 JHa 1i[Cz m 3H3 CH3 CH3 CH3 "CH3 3.--. HO(SiO 11 CH3NHCH2CH(OH3) CHgS iO SE10 SiOH2OH(OH3) CHgN'HOHg] 3H3 100 3HaJHa m 1H: ($113) F (3H; CH3 "CH :I 4.-.- HO SiO H CHaNHCHgCH(CH3)CHzSiOSiO SiCHgCH (CH CH2NHCH3 (3153 8-2 JH CHR R q JH linkages, aminoalkyl,aminophenyl, halo genophenyl and EXAMPLE 3 organosilyl radicals of thegeneral formula (XR'-)Y Si wherein Y is a monovalent hydrocarbon radicaland X is selected from the group consisting of halogen atoms having anatomic weight of at least and hydrogen atoms, R' is a divalent saturatedaliphatic hydrocarbon radical wherein the silicon atom is attached to acarbon atom which is at least the third and not more than the sixthcarbon atom away from the other substituent attached to R, R" is amonovalent hydrocarbon radical, a has a value of at least 1 and R is amonovalent hydrocarbon or a monovalent halogenated hydrocarbon radical,such as chloromethyl or 3,3,3-trifluoropropyl. These diorganosiloxanescan be used wherever conventional diorganosiloxanes are used. Thismethod of endblocking diorganosiloxanes is preferable to equilibratingsiloxanes because with this method only one species of siloxane isobtained.

The following examples are illustrative only and should not be construedas limiting the invention which is properly delineated in the appendedclaims.

EXAMPLE 1 3-chloro-2-methylpropyldimethylchlorosilane (556.5 g., 3 mols)and methylamine (640 g., 20.6 mols) were heated in a pressure vessel at100 C. for 22 hours. The mass was then cooled and the layers separated.Distillation of the top layer gave a 76 percent yield of Into a flaskcontaining 28.5 g. (0.2 mol) of the above product, there was added 1.8g. (0.1 mol) of distilled water. A peak temperature of 98 C. was reachedupon stirring the mass. Distillation at 2 mm. gave a 92 percent yield ofon [ortmnomomom CHgSi 0 3-chloro-2-methylpropyldimethylchlorosilane (371g., 2 mols) and ethylenediamine (840 g., 14 mols) were refluxed togetherfor 3 hours. The mass was then cooled and the layers separated.Distillation at 30 mm. pressure of the top layer gave a 75 percent yieldof NmoH-zorrmomomom ornsuom),

EXAMPLE 4 4-chlorobutyldimethylchlorosilane (115 g., 0.62 mol) andmethylamine (317 g., 10.3 mols) were heated in a pressure vessel at C.for 20 hours. The mass was then cooled and the layers separated.Distillation of the top layer gave a 35 percent yield ofCHzNCHzCHzCHgCHzSKCHa):

Into a flask containing 14.3 g. (0.1 mol) of the above product, therewas added 0.9 g. (0.05 mol) of distilled water. A temperature riseoccurred upon stirring the mass. A quantitative yield of CH3 [CHNHCHgCHgOH CH Si ]0 CH3 2 was obtained.

EXAMPLE 5 CH3NCH3CH(CH3)CH1S1(CH3) (C6115) EXAMPLE 6 3-chloropropyldimethylchlorosilane (342 g., 2 mols) and aniline (302 g.,14 mols) were heated in a flask for 3 hours at 100 C. The mass was thencooled and the aniline hydrochloride was partially separated by usingtriethylamine and toluene. Distillation at 15 mm. pressure gave a 21percent yield of CBHENCHZCHQCHZSKCHQQ EXAMPLE 7 An excess of ammonia wasbubbled through 3-chloro- 2-methylpropyldimethylchlorosilane (741 g., 4mols) in pentane. The resulting NH Cl was removed by filtration and thepentane was stripped from the product. 552 g. (1.76 mols) of and a 58percent yield of 8 EXAMPLE 8 The alkoxysilane,

CH NmoH oHmHomcHwm omsud 0H was heated to its atmospheric boiling pointand the methanol removed. Vacuum distillation of the remaining portiongave in a 68 percent yield.

Using the above procedure, the cyclic silane,

NHaoHzoHzlirofizomol-jn) onzsnocfl was produced from NHgOHzCHNHCHgCHflCH CH Si(O 0H EXAMPLE 9 The following cyclic silanes areproduced when the following halogenoalkylhalogenosilanes and aminocompounds are reacted in accordance with the procedure of Example 1. Thefollowing siloxanes are obtained when these cyclic silanes arehydrolyzed in accordance with the procedure of Example 1.

Table II Reactants Products Halogenoalkylenehalogenosilane AminoCompound Cyclic Silane Siloxane CzH5 1. C1CHzCH(CHa)CHg%i% CHaCHgCHzNHgCH3OH CHzNCHgCH(CHs)(2g???) CH3CHzCHzNHCH CH(CH 2 s z s 2 02115 CHaSi:IO

CH CH CH g:H[:CH, CH CHCH NH CH CHCH NCH (CH) CH S' [CH CHCH NHCH (CH)2. 2 3 2 1 2 Br 2( 2)s iC 3 a 2 a 2 2 3)z( 2) 2 z 2 a CH=CH5 CHzSl ICECH) CH r o H NH 0 H NoH (CH) CH s1 [0 H NHoH (OH) 0119 10 3, 1 a u 2 2 42 a 11 2 a 4 2 1 cm 8 (061111) H3) CH3 2 4. ClCHzCH(CHzCH3) NHzCHz(CH2)4NH2CH2(CH2)4CH2NCH2CH(CH3 [NHzCHz(CHz)4CHgNHCHz z oHs CHgNH omomsiqH,o.,H5

CH CH )CH3CH;S1(CH;C H5) (CH3) CH(CH CH3) CH2CH2%.H O

C H 5. ClCHgCH[(CHahCHflCHzggl NH20flH4NHg NHgCH4NCHgCHI(Cflflgglilggigfiiy [NH3C6H4NHCH2OH(OHZCHgOH a 1 a 3 Cal-I7CHgSi 0 CH CH CH )CH lSl OH NH CH NCH CH(CH )CH S' (CH )[CH NHCH CH(CH)CH ]S'O G1 a a i a i 1 a a 2 a a 1 6 z 3 0H; 2 001100311 CH3 7.C1CHzCH(CH3)CHz%i[l p-ClCaH NH2 ClCaH4NCHzCH(CHa)CHgS1(CHs)gO10fiH4NHCH2OH(C/H3)OH2 CH: 8. ClCHzCHgCHzSQifil CHaOCHgCHgNHgCHzCCHzCHgNCHgCHzCHzSl(CH3)2 CHaOCHgCHzNHCHgCHzCHz 3 CH3 Si 10 CH3 2Table Il-Continued Reactants Products HalogenoalkylenehalogenosilaneAmino Compound 7 Cyclic Silane iloxane (OHQOHQOCHE) 9. OIOHflCHgOHZSlOlCHBNH} CHzNCH CHgCH SKCHg) [CHaNHCHzCHzCH CH3 (CHZOHZOCHQ) 1 (CHzCHgOCH3) (OCHzCHgOCHa) CH3 10. ClCHaCHgCHgSiCl CHaNHz CHaNCH CH CH SKCHg) CHNHCH CH CHfiiO CHa (OOH2OH20CH3) (OCH OCHgCHz) 11. CiCHgCHzCHzSlOlCHaNHg CHaNCHzOHgOHgSi (CH3NHCHgCH CHz)SiO (OOHgOCHzCHa) (0 CHQOCH2CH3)2 EXAMPLE 10 When the following halogenoalkylhalogenosilanes areobtained when these cyclics are hydrolyzed in accordance with theprocedure of Example 1.

Table III Products fialogenoalkylhalogeno silanes Disilazanes CycliesSiloxane CHa L'ClCHaCHnCHzSiCl CH=C 2. Br(CHg) uSiBr CHs CH3 HN[SiCHzCHgCHgCl CaH5 2 H1 CH=CH2 HN siwmnBr A. HNCHzCHnCHzSl(CHa) (CoHs) lon I B. ClCH CHzCH Sl Ncmornomsi QXOGHQ CH3 A.[H2NCH2CHzCHzSi. 10

CH3 CHZCHzSi 1O CH=CH NEKCH 81 10 reacted with ammonia in accordancewith the procedure 50 "of Example 7, the following disilazanes areobtained. When these disilazanes are reacted with ammonia in accordancewith the procedure of Example 7, the following cyclic silanes areobtained. The following siloXanes are Table IV EXAMPLE 11 AlkoirysilanesProducts Cyclic alkoxysllanes Unit Formula of Siloxanes NHzCeHNHOHgCH(CH CHzSiO Table I V-Continued Alkoxysilanes Products Cyclicalkoxysilanes Unit Formula of Slloxanes HzN( 2)s i( Ha) H3):

CQHENCHZCH (CH5) CHzSi(O CuH5)l 1 onsmorrmsuom)(oomomo 0H9 C HNHOH,CH1(CH CHgSlOps OH: [HgN(CH2) 381 EXAMPLE 12 ing cyclic silanes arereacted with the following hydroxyendblocked siloxanes in accordancewith the procedure linkages, alkoxy, alkoxy radicals containing oxygenin the form of of Example 2. linkages and phenoxy radicals.

Table V Reactants Unit Formula of Siloxane Product Siloxane OyclicsllaneO'H ClLCF CH3 CH3 CH3 CHaOHrCFz HO S10 H C1CHgCH(CHa)CH2Si C1CHqCH(OH3)CHaSiNHCH GH (CH3) CHzSlO S10 C a mo 3 CH3 CH3 CH3 100 CH: CH SiOCH2CH(CH3)CHiNHSiCHflCH(CH3)CH1Cl NCH2OH(OH3)CH2S1(CH3)H CH3 CH Ca 1CBHE 03 CsHs HO SiO H NHgOHzCHgN(CHg)aSl(CaH) (CH3) NH CHzCHgNH(GH SiOSiO Si(CHz)aNHCH2CH1NH:

C 3 40o CH3 H3 400C 3 CH=CHg CH=CH5 CH=CH CH=CHg HO SiO HNHzCaH4N(CH2)uSi(CH=CHz) CH3 NHzCaH4NH(CHg)5SlO (SiO Si(CH2)aNHCgH4NHgCH: 250 CHa 0 we That which is claimed is: 2. The organosilicon compoundof claim 1, wherein 1. An organosilicon compound of the general formula(RNR)SiR wherein R is selected from the group consisting of hydrogenatoms, monovalent hydrocarbon, monovalent hydrocarbon radicalscontaining oxygen in the form of :-o-( 2- l l linkages, aminoalkyl,aminophenyl, halogenophenyl and organosilyl radicals of the generalformula wherein Y is a monovalent hydrocarbon radical and X is selectedfrom the group consisting of halogen atoms having an atomic weight of atleast 35 and hydrogen atoms, R is a divalent saturated aliphatichydrocarbon radical wherein the silicon atom is attached to a carbonatom which is at least the third and not more than the sixth carbon atomaway from the other substituent attached to R, and R" is selected fromthe group consisting of monovalent hydrocarbon, monovalent hydrocarbonradicals containing oxygen in the form of R is a monovalent hydrocarbonradical, R is a divalent saturated aliphatic hydrocarbon radical whereinthe nitrogen atom is attached to a carbon atom which is the third carbonatom away from the silicon atom and R" is a monovalent hydrocarbonradical.

3. An organosilicon compound of the formula CH NCH CH(CH )CHzSKCHa): 4.An organosilicon compound of the formula CHaNCHflCHgCHzCHgSKGHgh 5. Anorganosilicon compound of the formula oaHsNomonzcmsuom 6. Anorganosilicon compound of the formula OHBNCH2CH(OHH) z i(CHa) olin) 7. Amethod for making an organosilicon compound which comprises reacting (1)r 13 a a and (2) RNH wherein Ris selected from the group consisting ofmonovalent hydrocarbon, monovalent hydrocarbon radicals containingoxygen in the form of linkages, aminoalkyl, aminophenyl andhalogenophenyl radicals, R is a divalent saturated aliphatic hydrocarbonradical wherein the silicon atom is attached to a carbon atom which isat least the third and not more than the sixth carbon atomaway from theother substituent attached to R, and R is selected from the groupconsisting of monovalent hydrocarbon, monovalent hydrocarbon radicalscontaining oxygen in the form of linkages, alkoxy and phenoxy radicalsand alkoxy radicals containing oxygen in the form of linkages and X is ahalogen atom selected from the group consisting of chlorine, bromine andiodine, whereby an organosilicon compound of the formula (RNR)SiRz isobtained.

8. A method for making'the organosilicon compound of claim 2 whichcomprising reacting (1) [CICH CH (CH CH Si (CH C1 and (2) CH NI-Iwhereby the organosilicon compound of claim 3 is obtained.

10. A method for making an organosilicon compound of the general formulawhich comprises heating at a temperature in excess of 100 C. a compoundof the general formula (RNHR')Si(R"),,(OZ) wherein R is selected fromthe group consisting of hydrogen atoms, monovalent hydrocarbon,monovalent hydrocarbon radicals containing oxygen in the form oflinkages, aminoalkyl, aminophenyl and halogenophenyl radicals, R is adivalent saturated aliphatic hydrocarbon radical wherein the nitrogenatom is attached to a carbon atom which is at least the third and notmore than the sixth carbon atom away from the silicon atom and R isselected from the group consisting of monovalent hydrocarbon radicalsand monovalent hydrocarbon radicals containing oxygen in the form oflinkages and Z is selected from the group consisting of a I 14 p phenyland alkyl radicals and alkyl radicals containing oxygen in the form oflinkages and a has a value of from 0 to 2 inclusive.

11. The method of claim 10 wherein R is a monovalent hydrocarbonradical, R is a divalent saturated aliphatic hydrocarbon radical whereinthe nitrogen atom is attached to a carbon atom which is the third carbonatom away from the silicon atom and R" and Z are alkyl radicals.

12. Themethod of claim 10 wherein R is an alkyl radical of from 1 to 6inclusive carbon atoms, R is a -CH CH(CH )CH radical and R" and Z aremethyl;

13. A method for making a siloxane of the unit formula which compriseshydrolyzing and condensing a compound of the general formula wherein Ris selected from the group consisting of hydrogen atoms, monovalenthydrocarbon, monovalent hydrocarbon radicals containing oxygen in theform of I I a v linkages, aminoalkyl, aminophenyl, halogenophenyl andorganosilyl radicals of the formula (XR')Y Si where.- in Y is amonovalent hydrocarbon radical and X is selected from the groupconsisting of halogen atoms having an atomic weight of at least 35 andhydrogen atoms, R is a divalent saturated aliphatic hydrocarbon radicalwherein the silicon atom is attached to a carbon atom which is a leastthird and not more than the sixth carbon atom away from the othersubstituent attached to R, R is selected from the group consisting ofmonovalent hydrocarbon and monovalent hydrocarbon radicals containingoxygen in the form of o l I linkages, Z is selected from the groupconsisting of alkyl and phenyl radicals and alkyl radicals containingoxygen in the form of linkages and a has a value of from 0 to 2inclusive.

14. The method of claim 13 wherein R is a monovalent hydrocarbonradical, R is a divalent saturated aliphatic hydrocarbon radical whereinthe nitrogen atom is attached to a carbon atom which is the third carbonatom away from the silicon atom, R is a monovalent hydrocarbon radicaland Z is an alkyl radical.

15. The method of claim 13 wherein R is an alkyl radical of from 1 to 6inclusive carbon atoms, R is a CH CH(CH )CH radical, R" is an alkylradical of from 1 to 6 inclusive carbon atoms and Z is methyl.

16. A method for making an organosilicon compound which comprisesreacting (l) wherein R is selected from the group consisting of hydrogenatoms, monovalent hydrocarbon, monovalent hydrocarbon radicalscontaining oxygen in the form of inc-- I l linkages, aminoalkyl,aminophenyl, halogenophenyl and organosilyl radicals of the generalformula 15 wherein Y is a monovalent hydrocarbon radical and X isselected from the group consisting of halogen atoms having an atomicweight of at least 35 and hydrogen atoms, R is a divalent saturatedaliphatic hydrocarbon radical wherein the silicon atom is attached to acarbon atom which is at least the third and not-more than the sixthcarbon atom away from the other substituent attached to R, and R" is amonovalent hydrocarbon, and

H(s io 11 r wherein R is selected from the group consisting ofmonovalent hydrocarbon and monovalent halogenated hydrocarbon radicalsand a has a value of at least 1, whereby there is obtained anorganosilicon compound of wherein R, R, R", R and a are as abovedefined. v 17. A method for making an organosilicon compound whichcomprises reacting (1) wherein R is a monovalent hydrocarbon radical, Ris a divalent saturated aliphatic hydrocarbon radical wherein thenitrogen atom is attached to a carbon atom which is the third carbonatom away from-the silicon atom and R' is an alkyl radical, with (2)wherein R' is a monovalent hydrocarbon radical and a has a value of atleast 1, whereby there is obtained an organosilicon compound of theformula R! R!!! RI! wherein R. R. R". R' and a are as above defined.

18. An organosilicon compound of the general formula HN[Si(R") CH CH(CH)CH Clh wherein R" is a monovalent hydrocarbon radical.

19. An organosilicon compound of the formula Petrov et al.: Izvest.Akad. Nauk, SSSR, 1960, pages 143-5 (54, Chem. Abstracts, 20, 846).

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,146,250 August 25, 1964 John L. Speier It is hereby certified thaterror appears in the above numbered patent requiring correction and thatthe said Letters Patent should read as corrected below.

Column 1, lines 21 to 23 the formula should appear as shown belowinstead of as in the patent:

column 3, line 18, the formula should appear as shown below instead ofas in the patent:

line 49, the formula should appear as shown below instead of as in thepatent:

(RNHR -)Si [RfJ 02 line 59 for "ClCH CH(CH CH read ClCH CHUJH CH columns5 and 6, Table I, under the heading "Siloxane product" formula No. 2should appear as shown below instead of as in the patent:

Y 3 I S i S CH NHCH LHWH CHZilO $10 S|1CH CH(CH CH NHCH CH3-l CH 32 5 ICh columns 9 and 10, Table III, under the heading "Siloxane",

formula No. 2 A. should appear as shown below instead of as in thepatent:

CH;=...CH2 H N(CHZ s1 0 2 2 6 same columns Table IV, under the heading"Alkoxysilanes", the

third formula should appear as shown below instead of as in the patent:

columns 11 and 12, Table V, under the heading "Unit Formula of SiloxaneProduct", the second formula should appear as shown below instead of asin the patent:

e- 3 C6H5 NH CH CH NIKCH SiOfSiOl Si(CH NHCH CH NH Signed and sealedthis 15th day of June 1965 (SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner ofPatents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3 ,l46, 250 August 2 5, 1964 John L. Speier It is hereby certified thaterror appears in the above numbered patent requiring correction and thatthe said Letters Patent should read as corrected below.

Column 1, lines 21 to 23, the formula should appear as shown belowinstead of as in the patent:

column 3, line 18, the formula should appear as shown below instead ofas in the patent:

line 49, the formula should appear as shown below instead of as in thepatent:

n n line 59 for ClCH CH(CH CH read C1CH CH(CH )CH columns 5 and 6, TableI, under the heading "Siloxane product" formula No. 2 should appear asshown below instead of as in the patent:

i T t r- H f C I NHCH C (CH )CH i1O $10 SI 1CH CIHI(CI I )CH NHCH CH CH3Z5 CH columns 9 and 10, Table III, under the heading "Siloxane",

formula No. 2 A. should appear as shown below instead of as in thepatent:

one-1on H N(CH: Si 0 2 2 6 same columns, Table IV, under the heading"Alkoxysilanes", the third formula should appear as shown below insteadof as in the patent:

e ii H NC H NHCH CH(CH )CH S1(OC H columns 11 and 12, Table V, under theheading "Unit Formula of Siloxane Product", the second formula shouldappear as shown below instead of as in the patent:

(3 H c H c 11 NH CH CH NEKCH SiO'LSiC Si(CH NHCH CH NH Signed and sealedthis 15th day of June 1965.

(SEAL) Attest:

Ei RNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of.Patents

1. AN ORGANOSILICON COMPOUND OF THE GENERAL FORMULA
 7. A METHOD FORMAKING AN ORGANOSILICON COMPOUND WHICH COMPRISES REACTING (1)
 10. AMETHOD FOR MAKING AN ORGANOSILICON COMPOUND OF THE GENERAL FORMULA
 13. AMETHOD FOR MAKIG A SILOXANE OF THE UNIT FORMULA
 18. AN ORGANOSILICONCOMPOUND OF THE GENERAL FORMULA HN(SI(R"'')2CH2CH(CH3)CH2CL)2 WHEREIN R"IS A MONOVALENT HYDROCARBON RADICAL.